Process and compositions for dry cleaning



Patented Nov. 14, 196? 3,352,790 PRGCESS AND COMPQSITHQNS FQR DRY CLEANING Jeal Sugarman, Flushing, N.Y., and Fred E. Woodward, Watchung, Plainiield, N.J., assignors to General Aniline & Film Corporation, New York, N.Y., a corporation of Delaware No Drawing. Filed Feb. 21, 1964, Ser. No. 346,414 16 Claims. (Cl. 252-471) This invention relates to improvements in the dry cleaning of fibrous textiles and related materials and more particularly to new and improved compositions for use with dry cleaning solvents, and to processes of dry cleaning wherein said improved compositions are employed.

It is well known that many types of fabrics and materials cannot be cleaned by the ordinary means of soap or detergents and water, such as are employed in laundering type operations since the presence of water deleteriously affects such materials. To provide effective cleaning for such materials, a dry cleaning process must be used. Dry cleaning processes employ organic solvents which are effective in removing from the materials treated most of the undesirable dirt, grease, dust and the like. It is also a common expedient in dry cleaning processes to add a small amount of water which, sufficiently dispersed in the dry cleaning fluid, will be effective to remove watersoluble stains without adversely affecting the materials treated.

It is therefore an object of this invention to provide new compositions, particularly suitable for use in dry cleaning operations.

It is a further object of this invention to provide new compositions suitable for use in all of the generally employed dry cleaning solvents.

It is a still further object of this invention to provide new compositions which give outstanding and improved cleaning ability by virtue of an outstanding detergency action coupled with an excellent ability to prevent soil redeposition on the materials treated.

It is another object of this invention to provide an improved process of dry cleaning in all types of dry cleaning solvents.

It is a further object of this invention to provide an improved process of dry cleaning wherein the usual dry cleaning solvents are employed in conjunction with minor amounts of water.

The compositions of the present invention comprise the usual organic dry cleaning solvent and a phosphate ester of a non-ionic surfactant hereinafter to be more fully described. In addition, other surfactants may be present as well as a small amount of Water, e.g., 0.1 to about 10% Among the dry cleaning solvents one may use and which are normally employed in the dry cleaning industry are the following:

fiuoro carbons e.g., trichlorotrifluoro ethane naphtha trichloroethylene tetrachloroethylene perchloroethylene carbon tetrachloride Stoddard Solvent, flash point 100 F. Stoddard Solvent, flash point 140 F.

The phosphate esters of non-ionic surfactants which are herein contemplated are monoand diphosphate esters and mixtures thereof which non-ionics contain from about 1 mole up to about 75 to 95% weight percent of alkylene oxide. The alkylene oxides or precursors thereof which may be employed to yield the corresponding oxyalkylene groups in the non-ionic surface active agents are those which contain from 2 to 4 carbon atoms such as ethylene oxide, propylene oxide, butylene oxide, butylene dioxide, epichlorohydrin, isobutylene oxide, and the like. Since it is essential that the phosphate esters herein contemplated have solubility of a significant amount as hereinafter disclosed in the hydrocarbon or chlorinated hydrocarbon drycleaning solvent, the upper limit of ethylene oxide which may be used is about 7.5% by weight based upon the weight of the non-ionic surfactant. Above this amount the ethylene oxide condensates are too hydrophilic to have the requisite solubilities. With oxyethylene groups containing 3 carbon atoms, e.g., derived from propylene oxide, up to about by weight thereof may be combined in the nonionic surfactant. Using oxyyalkylene groups containing 4 carbon atoms such as derived from the interaction with butylene oxide up to about of such grouping based upon the total weight of non-ionic surfactant may be employed. In addition, it is clear and obvious that mixtures of such oxyethylating reagents may be used whereby there results in the non-ionic surfactant variations in the oxyalkaline groups.

The non-ionic oxyalkylated products which are herein contemplated as precursors for the phosphate esters are Well known in the art and are derived from a reactive hydrogen compound and the alkylene oxide as, for example, disclosed in Us. Patents 2,213,477 and 1,970,578. in general, the reactive hydrogen compound is a hydrophobic moiety such as a phenol, alkylated phenol, thiophenol, higher alcohol, higher mercaptan, higher alkyl or aryl amide, higher alkyl or aryl sulfonamide, and the like containing a least about 8 carbon atoms. The reactive hydrogen compound may be a propylene or butylene oxide polymer (e.g., M.W. 400 to 4000), or the reaction product of an amine, e.g., ethylenediamine or an alcohol or phenol or the like with propylene or butylene oxide. The following illustrate some typical reactive hydrogen compounds suitable for reaction with ethylene oxide to yield non-ionic surfactants as precursors for the instantly contemplated phosphate esters:

nonylphenol (propylene trimer) octylphenol (diisobutylene) dodecylphenol (propylene tetramer) diamylphenol dibutylphenol alkylphenols, where alkyl is C; to C 'olypropylene oxide of M.W. 400 to 25 I NCH CH NH -}-propylene oxide to M.W. 800 to 2500 (NH or X(NH) +propylene oxide to M.W. 400 to 2500 (-OH or X(OH) +propylene oxide to M.W. 800 to 2500 (:residue of active hydrogen compound The above types of compounds are then reacted with thylene oxide and the like to yield the non-ionic used to vrepare the phosphate esters.

The phosphate esters used in the present invention may be prepared by numerous techniques. The preferred nethod involves the reaction of one mole of P 0 with l to 4.5 moles of the non-ionic surfactant as described lIld claimed in US. Patent 3,004,056 by Nunn and Hense [1141 US. Patent 3,004,057 by Nunn. As described in he said Nunn and Hesse patent, the reaction between he P 0 and the non-ionic polyoxyalkylene ether is :onducted under substantially anhydrous conditions and at a temperature below about 110 C. In its perferred ?orm, the reaction is carried out by adding the P 0 gradually, with vigorous agitation to the non-ionic sur- Face active agent in liquid form. The reaction is exohermic and cooling is in some cases necessary to keep he temperature below 110 C., since discolored and larkened products tend to be produced above this temaerature. The reaction proceeds continuously during the iddition of the P 0 and is preferably followed by mainvenance of the reaction mixture at ambient temperatures 1p to 110 C. for an additional period of time after :ompletion of such addition to allow for complete solu- :ion of the P 0 and reaction with the non-ionic surface active agent.

The exact chemical constitution of the products proiuced by the above described reaction is not definitely known in view of the recognized tendency of the P 0 to form complex products and polymers in such reactions with hydroxylic compounds. In general, the product will usually contain about to 45% of the secondary phosphate ester of the non-ionic agent, to 80% of the primary phosphate ester, 0 to of unreacted non-ionic agent, and small amounts of unidentiied by-products.

The following examples illustrate the preparation of such phosphate esters.

Example A 2.7 moles of a non-ionic surface active compound derived from dinonyl phenol condensed with 4 moles of ethylene oxide is reacted with 1 mole of P 0 in the manner described in the examples of US. Patent 3,004,- [)56. The product consists of about equal amounts of mono and di-ester with about 10-15% unreacted nonionic.

Example B The procedure of Example A is repeated except that the non-ionic compound is derived from the interaction of nonyl phenol with 1.5 moles of ethylene oxide (ethylene oxide content of condensate 29.2%).

Example C The procedure of Example B is repeated except that 6.0 moles of ethylene oxide are condensed to yield a. non-ionic containing 54.5% etthylene oxide.

Example D Example B is again repeated except that about 10 moles of ethylene oxide are reacted to yield a condensation product containing about 64% ethylene oxide.

Example E Example A is again repeated except that the reaction is carried out between tridecyl alcohol (obtained by the oxo process from using triisobutylene) and 9.75 moles of ethylene oxide to yield a product containing 68% ethylene oxide.

Example F The procedure of Example A is repeated except that the non-ionic is a dodecyl phenol plus 2 moles of ethylene oxide condensate.

Example G The procedure of Example A is again repeated employing as the non-ionic surface active agent a dinonyl phenol plus 5 moles ethylene oxide (40% ethylene oxide content).

Example H The procedure of Example A is once again repeated employing as the surfactant a dinonyl phenol plus 7 moles ethylene oxide (47% ethylene oxide content).

Example I The procedure of Example A is still once again repeated employing as the non-ionic surface active agent dinonyl phenol reacted with 1.5 moles of ethylene oxide to yield non-ionic product containing about 20% ethylene oxide.

Example J The above procedures are again repeated using as H the non-ionic procedure the condensation product of dodecyl phenol with 1.8 moles of ethylene oxide.

Example K In the following examples the procedure of Example A is reptated using the indicated non-ionic compounds:

iso-otcyl alcohol+2.5 E.O. nonyl alcohol-H E.O. dodecyl mercaptan-l-Z E.O. dodecyl mercaptan+9 E.O. cetyl mercaptan+4 E.O. dinonyl phenol+9.6 E.O. dinonyl thiophenol+6 E.O. soya bean oil amine+l0 E.O. resin amine-[-15 E0.

iso-octyl amine-+8 E.O. dodecyl benzene sulfonamide+l0 E.O. decyl sulfonamide+6 E.O. oleic acid+15 E.O. stearic acid+12 E.O. stearamide+8.5 E.O. tetradecylbenzamide+12 E.O. polypropylene glycol (average M.W.=750) +2 E.O. l8) polypropylene glycol (average M.W.=4-00) +6 BO. (19) dinonyl phenol-(-15 E.O.

By carrying out the above reaction in the presence of a small amount of a phosphorus-containing compound selected from the group consisting of hypophosphorous acid, salts of hypophosphorous acid, phosphorous acid, and salts and esters of phosphorous acid, preferably sodium hypophosphite or hypophosphorous acid, as described in said Nunn 3,004,057 patent, lighter colored or substantially colorless reaction products are obtained.

While the presence of unreacted non-ionic is not detrimental to the attainment of the objects of the present invention, the amount of non-ionic can be reduced, if desired, to a minimum of less than about 10% by incorporating in the reaction mixture, a small amount of mineral acid such as phosphoric acid, hydrochloric acid or sulfuric acid. Since phosphorous pentoxide yields phosphoric acid in the presence of water, the latter can advantageously and preferably be used to form the acid in situ. With the use of the mineral acid the amount of phosphorous pentoxide can also be increased to as much as 3 moles per mole of non-ionic reactant, thereby favoring the formation of the monoester in major amounts, i.e., substantially no diester.

Monoesters and diesters can also be prepared from the corresponding triesters by reacting the triester with phosphoric acid. By varying the ratio of non-ionic to acid, one can prepare either monoor diester to the substantial exclusion of the other. A high ratio of triester to acid (2:1) produces diester whereas a low ratio (0.511) produces monoester.

Example L Equimolar amounts of the non-ionic surface active compound of Example A and phosphorous pentoxide are heated at 90 C., while adding in the presence of about 0.4% water the P over a period of one hour. Then the reaction mixture is heated for 4 hours at 125 C. The final product is a monoester.

Example M Example L is repeated employing one mole of a dodecyl phenol plus 2 moles ethylene oxide condensate and two moles of P 0 The final product is a monoester.

Example N Example L is again repeated using the following nonionics:

A. octadecanol+3 moles ethylene oxide B. hexadecanol+4 moles ethylene oxide C. 1-eicosoanol+6 moles ethylene oxide D. l-doctriacontenol-l-7 moles ethylene oxide E. dodecyl phenol+5 moles ethylene oxide F. hexadecyl phenol-F3 moles ethylene oxide -G. tri-n-octyl phenol+4 moles ethylene oxide H. tri-n-octyl phenol-l-S moles propylene oxide I. dodecyl phenol+3 moles propylene oxide J. dinonyl phenol-{-15 moles propylene oxide K. diisohexyl phenol+2 trnoles propylene oxide L. tri-n-butyl phenol+2 moles propylene oxide M. tri-n-butyl phenol+3 moles propylene oxide N. tri-n-butyl phenol+4 moles propylene oxide 0. tri-n-butyl phenol+3 moles ethylene oxide P. hexadecanol+3 moles propylene oxide Q. octadecanol+4 moles propylene oxide R. butyl hexyl phenol-k4 moles ethylene oxide S. ethyl heptyl phenol+5 moles ethylene oxide T. ethyl heptyl phenol+3 moles propylene oxide U. ceryl alcohol+2 moles ethylene oxide V. l-octacosanol-it moles ethylene oxide W. 1-nonacosanol+7 moles ethylene oxide X. l-triacontenol-l-fi moles ethylene oxide Y. 1-tetratriacontenol+5 moles ethylene oxide Z. l-tetratriacontenol-l-Z moles propylene oxide Example 0 A phosphate triester of the non-ionic compound of Example A is prepared by reacting 3 moles of said non-ionic with 1 mole of phosphorous oxychloride in the presence of 1 mole of pyridine and 100 ml. of benzene. The POCl is added dropwise to the other components at a temperature of about 0 C. and the temperature is held below C. After all of the POCl has been added, the mixture is refluxed for 3 hours and then the solvent is removed under vacuum distillation. The triester results.

The triester is converted to a monoester by adding 1 mole of phosphoric acid to 0.5 mole of the triester at about room temperature. The monoester results.

Example P Example 0 is repeated except that 2 moles of triester are used in lieu of 0.5 mole. The diester results.

The monoand di-phosphated products may be represented by the following formulae:

wherein R represents H, methyl, ethyl, etc.; R represents the reactive hydrogen compound; X may be hydrogen or alkali metal, alkaline earth metal, ammonium, or amine (water soluble or insoluble) preferably lower aliphatic including hydroxyamines; and n=number of moles of alkylene oxide necessary to yield a final product containing 5 to by weight thereof; mathematically this may be represented as follows:

where R is the reactive hydrogen compound.

The phosphate esters which are herein contemplated are possessed of the following outstanding and desirable characteristics which are important in dry cleaning:

(1) They are readily soluble in the two types of solvents currently being used for dry cleaning, namely, Stoddard Solvent and perchloroethylene.

(2) They promote excellent carbon soil detergency and anti-redeposition properties by themselves in the two solvents.

(3) They are compatible with non-ionic and anionic surfactants and most organic solvents employed in dry cleaning thus rendering them suitable for formulating, if desired.

(4) They are manufactured in the form of free acids, thus oifering wide latitude in both degree of neutralization and in selection of base used for neutralization. Among the bases which can be used are the following: sodium hydroxide, potassium hydroxide, barium hydroxide, methylamine, isopropulamine, ethylene diamine, various ethoxylated and unethoxylated fatty amines such as tall oil amine, soya amine, oleylamine, imidazolines, and

, aminoamides.

(5) They are extremely light in color, odorless and not subject to rancidity or breakdown. Consequently, no detrimental effects on fabrics can result due to these causes.

(6) The phosphate esters are excellent anti-static agents and so will reduce the danger of static charge build-up. This is important in the case of petroleum based solvents in the dry cleaning process.

(7) These products have the ability to solubilize certain amounts of moisture which is necessary in dry cleaning for the removal of water soluble stains such as salt and sugar.

(8) Only small amounts of water are necessary to effect outstanding removal of water-soluble products. This is important where larger amounts of water would cause shrinkage of woolens and the like.

The compositions of the present invention comprise from about 0.2 to about 10 parts by weight of the phosphate ester and 90 to 99.8 parts of the solvents. In a more concentrated form the compositions comprise 20- 80 parts (or even parts) by weight phosphate ester and 20-80 parts of a suitable vehicle in which the phosphate ester is soluble. In each instance the total parts should be 100.

The formulations hereinafter to be described where specific data is indicated for detergency and redeposition characteristics are tested as follows: 50 ml. of phosphate ester is dissolved in 50 ml. of selected dry cleaning solvent. 4 ml. of this concentrate is diluted to 100 ml. with the same solvent. To this 100' ml. in a mason jar there re added 50 A" steel balls, one 3%" x 4" clean woolen Watch and one 3%" x 6" carbon soiled woolen swatch nd then agitated in a Launderometer for /2 hour at aom temperature. The swatches are rinsed in fresh solent and dried. Reflectance readings are taken before and fter cleaning by means of a Photovolt Reflectorneter, 10(161 610. In the examples, the detengency values are xpressed as increase in reflectance units of the clean watch over the soiled swatch so consequently a higher alue indicates increased soil removal. Conversely, reeposition figures are expressed as decrease in reflectance mits of the clean swatch before and after the dry cleann-g cycle so a lower figure indicates increased anti-soil edeposition properties.

In the following examples which are by way of illusration only, parts are by weight unless otherwise indiated.

Example 1 50 ml. of the sodium salt of a phosphate ester prepared LS described below is dissolved in 50 ml. of Stoddard lolvent: then 4 ml. of this concentrate is diluted to 100 nl. with Stoddard Solvent. This diluted solution is then lsed to test a carbon soiled woolen swatch for detergency tl'ld a clean woolen swatch for redeposition as described tbove.

A. Preparation of phosphate ester.2.7 moles of a ionylphenol (propylene trimer) condensate with 9.5 noles of ethylene oxide is reacted with 1 mole of P 11 the presence of sodium hypophosphite iollowinlg the Jrocedure described in the said N-unn US. Patent 3,004,- )57. The product consists of about equal amounts of nonoand di-ester with about -15% residual unreacted ion-ionic. Sodium hydroxide is used to neutralize the free acid and bring the pH to about 7.0 whereby the ;odi-um salt is formed. The detergency in the Stoddard Solvent shows an increase of 13.0 reflectance units and Eor redeposition a decrease of 7.9 units. In the following table a comparison with other detergents is shown.

TABLE I Detergenoy Redeposition (a) Example 1 13.0 7.9 (b) Dinonyl phenol plus moles ethylene oxide 9.6 14. 2 {0) Nonyl phenol plus 6 moles ethylene oxide 0. 6 40.1 (d) Isopropylamine dodecyl benzene sulfonate 11.4 9. 0 (e) Commercial Product A. 12.1 9.8 (1) Commercial Product B 10. 9 10.9

From the above it is evident that the product of Example 1 is superior to all of the others in redeposition and detergency characteristics.

Example 2 Example 1 is repeated except that perchloroethylene is used as the solvent. In Table II the results are given, and a comparison with products (13) through (8) 0f Again it is clear that in perchloroethylene the product of Example 2 is far superior to all others in redeposition characteristics and much better than the others in detergency value. Only product (e) comes close to Example 2 in detergency but here redeposition is far poorer in the competitive product.

Example 3 TABLE III Detergeney Redeposition Product Perchloro- Stoddard Perchloro- Stoddard ethylene ethylene 22. 0 14. 5 6. 3 4. 9 14.3 9.6 17.8 14. 2 l3. 1 0. 6 18. 9 40. 1 15. 4 11. 4 10. 1 9. O 18. 2 12. 1 8. 7 9. 8 13. 1 l0. 9 16. 9 10. 9 12. 4 20. 5 10. 5 13. 0 16. 5 9. 0

Example 4 Examples 1 and 2 are again repeated employing 3 moles of a non-ionic derived from dinonyl phenol and 7 moles of ethylene oxide reacted with 1 mole of P 0 and converted to the sodium salt by neutralizing with 50% NaOH to a pH of about 6.5. The detergency and redeposition values are:

Detergency Redeposition Perchloroethylene 19. 2 2. 4 Stoddard Solvent 15.9 2. 2

Example 5 Examples 1 and 2 are once again repeated employing the phosphate ester sodium salt (from nonionic to P 0 ratio of 2.7: l) of a nonionic derived from nonyl phenol A phosphate ester (nonionic to P 0 ratio of 2.721) of a nonionic derived from dodecyl phenol and 6 moles of ethylene oxide is used in the form of the sodium salt to repeat Examples 1 and 2. The results are:

Detergency Redeposltion Perchloroethylene 18. 9 4. 7 Stoddard Solvent 1G. 4 4. 2

Example 7 Examples 1 and 2 are once again repeated employing the sodium salt of a phosphate ester (from nonionic to P ratio of 2.721) of a nonionic derived from dinonyl phenol and moles of ethylene oxide. The results are:

Detergency Redeposition Example 8 Example 1 is repeated except that the laundering cycle is 1-0 minutes and t e phosphate ester sodium salt is derived from a noni nic to P 0 ratio of 27:1 and the nonionic is prepared from tridecyl alcohol and 7 moles of ethylene oxide. The results are:

STODDARD SOLVENT Detergency ll Redeposition 3 Example 9 Example 8 is repeated at a concentration of 1% (rather than 2%). Results are:

Detergeney ll Redeposition 2 Example 10 Examples 8 and 9 are repeated employing the isopropylamine salt in lieu of the sodium salt. Results are:

Concentration, percent Detergency Redeposition Example 11 Examples 8, 9 and 10 are repeated employing the salts of phosphate ester (nonionic to P 0 ratio :1) of a nonionic derived from dinonyl phenol and 9.5 moles of ethylene oxide. Results are:

Concentration, Salt Detergency Redeposition percent 12 l o 11 0 Isopropylarnine 10 1 do 10 0 In the following table the results of Examples 8-11 are tabulated and compared with solvent alone and the salts of dodecylbenzene sulfonate:

Example 12 Examples 1 and 2 are again repeated employing the following nonionics:

Percent alkylene Nonionic: oxide A. Nonyl phenol 15 moles ethylene oxide 75 B. Nonyl phenol 5+ 4 moles ethylene oxide 44 C. Dinonyl phenol 24 moles ethylene oxide 75 D. Dodecyl phenol f+ 10 moles ethylene oxide 63 E. Tri-octadecyl phenol 1 mole ethylene oxide 5 F. Trio'ctadecyl phenol 30 moles ethylene oxide 61 G. Dinony-l phenol 2 moles ethylene oxide 20 H. Hexadecyl phenol 1+ 3 moles ethylene oxide 30 I. Nonyl phenol 5+ 1 mole ethylene oxide 17 I. Lauryl alcohol 4 moles ethylene oxide 49 K. Decyl mercaptan 5 moles ethylene oxide 56 L. Oleyl mercaptan 10 moles ethylene oxide 61 M. Octylamine 8 moles ethylene oxide 73 N. Oleic sulfamide 4 moles ethylene oxide 40 O. Oleic acid anilide 5+ 20 moles ethylene oxide 71 P. Lauric acid amide 5+ 3 moles ethylene oxide 40 Q. Dibutyl naphthalene sulfamide I+ 10 moles ethylene oxide 58 R. Tributyl phenol 1+ 7 moles ethylene oxide 54 Example 13 The reactive compounds, i.e., the phenols, alcohol, mercaptans, amine, amides and sulfamides, of Example 12 are reacted With varying molar amounts of 1,2-pro- TABLE IV Percent Reactive Compound Oxyalkylating Agent Alkylene Oxide Nonyl phenol 5 moles propylene oxide 57 Do 10 moles propylene oxide 73 Do. 20 moles propylene oxide 84 Do. 5 moles bntyleue oxide. 62 Do 1 mole butylene oxide. 25 Do. 11 moles bntylene oxide. 79 Do. 25 moles butylene oxide. 89 Do 35 moles butylene oxide 92 n-Octyl phenolv 95 Dinonyl phenol 51 Do 68 Dodecyl phenol. 63 Tributyl phenol... 63 Lauryl alcohol. 7O 'Iridecyl alcohol... 69 Tributyl phenol. 53 Do. 69 Do. 77 Do. 58 Do. 77 Do 84 Deeyl mercaptan 10 moles propylene oxid 77 o 20 moles propylene oxide. 87 o 10 moles hutylene oxide. 80 Octyl amine. 10 moles propylene oxide. 82 o 10 moles bntylene oxide 85 Laurie acid amide ..do 78 Example 14 Example E is repeated except that 6 moles of ethylene are used and the final product contains 56.9% ethylene oxide.

Example 15.-Preparation of magnesium salts The phosphate ester products of Example K-6, EX- ample 3 and Example 14, in free acid form in amounts of 844 g., 697 g. and 797 g., respectively, are added in separate vessels to 844 g., 697 g. and 797 g., respectively, of Stoddard Solvent. To the first two vessels there are added Example 15 is repeated except that the solvent is per- :hloroethylene.

Example 17 The detergency and redeposition tests of Examples 1 and 2 are repeated using the following phosphate esters:

. disodium salt of ester of Example L.

diammonium salt of ester of Example M.

. disodium salt of ester of Example N-E.

. isopropylamine salt of ester of Example NI.

magnesium salt of ester of Example N]. magnesium salt of ester of Example L.

monoethanolarnine salt of ester of Example L. H. diethanolamine salt of ester of Example L.

I. monosodium salt of ester of Example P.

1. magnesium salt of ester of Example P.

came s Excellent and comparable results are obtained.

The following formulations illustrate 100% active concentrates which are neutral, water-white, clear liquids:

A. 90 parts free acid of the phosphate ester (nonionic to P ratio of 2.7: 1) of a nonionic derived from nonyl phenol and 9.5 moles of ethylene oxide, and 11 parts isopropylamine.

B. 95 parts free acid of the phosphate ester (nonionic to P 0 ratio of 4.0:1) of nonionic derived from nonyl phenol and 6 moles ethylene oxide, and 10 parts isopropylamine.

C. 92.5 parts free acid of the phosphate ester (nonionic to P 0 ratio 3.021) of nonionic derived from dinonyl phenol and 9.5 moles of ethylene oxide, and 7 parts isopropylamine.

D. 92 parts free acid of the phosphate ester (nonionic to P 0 ratio 27:1) of nonionic derived from tridecyl alcohol and 7 moles of ethylene oxide, and 13 parts isopropylarnine.

In addition to the amine salts which are specifically described and exemplified above, other amine salts and hydroxyamine salts may be used including salts of ethylene diavmine, 1,2-pr0pylene diamine, 1,4-butylene diamine, methyl ethyl amine, methyl isopropyl amine, ethyl iso- .propyl amine, diisopropyl amine, 2-aminoethanol, triethanol amine, 3-aminopropanol, and the like.

Other variations in and modifications of the described processes which will be obvious to those skilled in the art can be made in this invention without departing from the scope or spirit thereof.

We claim:

1. A dry cleaning detergent composition comprising (a) from about 90 to 99.8 parts by weight of a dry cleaning solvent and,

(b) as the detergent from about 0.2 to about 10 parts by weight of a phosphate ester of a nonionic surface active agent, said ester being selected from the class consisting of monoand di-phosphate esters and mixtures thereof, in their free acid form, sodium salt form or amine salt form; said non ionic surface active agent having the molecular configuration of a condensation product of (1) an organic compound containing a reactive hydrogen atom selected from the group consisting of ROH, RAH, R-COOH, RNH

and RSO NH compounds, wherein R is a hydrocarbon radical of from 8 to 60 carbon atoms, and

(2) at least one mole of an alkylene oxide containing 2 to 4 carbon atoms and up to about -95 weight percent of total combined alkylene oxide, the upper limit of 75% for ethylene oxide, an upper limit for propylene oxide and the upper limit for butylene oxide.

2. A dry cleaning detergent composition as defined in claim 1 wherein the detergent is derived from an alkyl phenol and ethylene oxide.

3. A dry cleaning detergent composition as defined in claim 2 wherein the alkyl phenol is nonly phenol.

4. A dry cleaning detergent composition as defined in claim 2 wherein the alkyl phenol is octyl phenol.

5. A dry cleaning detergent composition as defined in claim 2 wherein the alkyl phenol is dodecyl phenol.

6. A dry cleaning detergent composition as defined in claim 2 wherein the alkyl phenol is dinonyl phenol.

7. A dry cleaning detergent composition as defined in claim 1, wherein the detergent is derived from a fatty alcohol and ethylene oxide.

8. A dry cleaning detergent composition as defined in claim 7 wherein the fatty alcohol is lauryl alcohol.

9. A dry cleaning detergent composition as defined in claim 7 wherein the fatty alcohol is oleyl alcohol.

10. A dry cleaning detergent composition as defined in claim 7 wherein the fatty alcohol is tridecyl alcohol.

11. A dry cleaning detergent composition as defined in claim 1 wherein the dry cleaning solvent is a petroleum based hydrocarbon.

12. A dry cleaning detergent composition ,as defined in claim 1 wherein the dry cleaning solvent is Stoddard Solvent.

13. A dry cleaning detergent composition as defined in claim 1 wherein the dry cleaning solvent is a chlorinated hydrocarbon solvent.

14. A dry cleaning detergent composition as defined in claim 1 wherein the dry cleaning solvent is perchloroethylene.

15. A dry cleaning detergent composition as defined in claim 1 wherein the dry cleaning solvent is a petroleum based hydrocarbon solvent and the nonionic surface active agent is a polyoxyalkylene ether of an alkyl phenol.

16. A dry cleaning detergent composition as defined in claim 1 wherein the dry cleaning solvent is a chlorinated hydrocarbon solvent and the nonionic surface active agent is a polyoxyalkylene ether of an alkyl phenol.

References Cited UNITED STATES PATENTS 1,970,578 8/1934 Schoeller et al. 25289 2,941,952 6/1960 Lewis et a1. 252171 X 3,004,056 10/1961 Nunn et a1. 25289 X 3,117,152 1/1964 Michaels 25217l XR 3,162,604 12/1964 Michaels 252- 171 LEON D. ROSDOL, Primary Examiner.

JULIUS GREENWALD, Examiner.

J. T. FEDIGAN, Assistant Examiner. 

1. A DRY CLEANING DETERGENT COMPOSITION COMPRISING (A) FROM ABOUT 90 TO 99.8 PARTS BY WEIGHT OF A DRY CLEANING SOLVENT AND, (B) AS THE DETERGENT FROM ABOUT 0.2 TO ABOUT 10 PARTS BY WEIGHT OF A PHOSPHATE ESTER OF A NONIONIC SURFACE ACTIVE AGENT, SAID ESTER BEING SELECTED FROM THE CLASS CONSISTING OF MONO- AND DI-PHOSPHATE ESTERS AND MIXTURES THEREOF, IN THEIR FREE ACID FORM, SODIUM SALT FORM OR AMINE SALT FORM; SAID NON IONIC SURFACE ACTIVE AGENT HAVING THE MOLECULAR CONFIGURATION OF A CONDENSATION PRODUCT OF (1) AN ORGANIC COMPOUND CONTAINING A REACTIVE HYDROGEN ATOM SELECTED FROM THE GROUP CONSISTING OF R-OH, R-SH, R-COOH, R-NH2'' 